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Influence of bases on heterogeneous Lewis acid catalyzed hydrogen transfer reactions
Veselá, Klára ; Přech, Jan (advisor) ; Bulánek, Roman (referee)
Heterogeneous Lewis acid zeolites catalyzed Meerwein-Ponndorf-Verley (MPV) reduction (transfer hydrogenation), where ketones and aldehydes are reduced to the corresponding alcohols. The hydrogen is taken from a secondary alcohol. These Lewis acid zeolite catalysts have a great advantage over homogenous catalysts as they are well separable from the reaction mixture and recyclable. Lewis acid zeolites are materials that contain incorporated tin or zirconium species, which act as Lewis acid sites. MPV reduction of citronellal provides citronellol as a product. However, the reaction of citronellal with 2- propanol also proceeds via a parallel reaction pathway providing isopulegol as the major product. Addition of pyridine (an organic base) to the reaction mixture switches the selectivity of the reaction, i.e., citronellol becomes the main product of the cited citronellal reaction with 2-propanol. It was investigated whether this phenomenon would also be observed for reactions with the addition of different bases. To answer these questions, Sn-BEA and Zr-BEA were prepared by hydrothermal synthesis. Impreg-Zr-BEA and impreg-Sn-BEA were prepared by postsynthesis metal incorporation. In addition, highly porous 2D Self-pillared pentasil zeolites containing tin and zirconium were hydrothermally synthesized....
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The effect of substituents, structure of the reactant and type of active sites on the reaction rate and selectivity of cyclization reactions
Živný, Marek ; Veselý, Ondřej (advisor) ; Bulánek, Roman (referee)
Tetrahydropyrans (THPs) are valuable compounds in the synthesis of pharmaceuticals and fragrances. Currently, THPs are most commonly synthesized using the Prins cyclisation, hetero-Diels-Alder reaction and oxy-Michael reaction. These reactions are undesirable because they use catalysts based on heavy metals and strong acids, which are harmful to the environment. In this thesis, we investigated the synthesis of THPs with the aim of replacing toxic heavy metals and strong acids with more benign catalysts, such as zeolites. Zeolites are microporous crystalline metallosilicates, which are commonly used as catalysts due to their high acidity, selectivity and stability. Previous research has successfully shown that zeolites can catalyse THP synthesis through cyclisation of unsaturated alcohols and determined the effect of pore size on catalytic activity. In contrast, this work aimed to examine zeolites with different framework elements, which introduce diverse types of acid sites. Additionally, we aimed to investigate the impact of functional groups present in the structure of the reactants, specifically functional groups with either electron-donating (EDG) or electron-withdrawing (EWG) effects and with different aromatic cycle systems. We chose (E)5-phenyl-4-pentenol as the primary reactant for the cyclisation....
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Deposited palladium catalysts
Semler, Miloslav ; Štěpnička, Petr (advisor) ; Balcar, Hynek (referee) ; Bulánek, Roman (referee)
Palladium catalysts are frequently used in C-C coupling reactions. The aim of this work is to prepare several heterogeneous palladium catalysts from comercially available silica gel, each with different bifunctional ligand deposited on the surface of silica gel by N-propylamide linking group, and their testing on several C-C coupling reactions (Heck reaction, reaction of acyl chlorides with boronic acids and reaction of acyl chlorides with terminal acetylenes). Some other aspects of heterogeneous catalysis (such as palladium leaching into the reaction mixture and possibility of catalyst reuse) are discussed, too. Powered by TCPDF (www.tcpdf.org)
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Heterogeneous catalysis of terpenoid redox reactions
Kurucová, Svetlana ; Přech, Jan (advisor) ; Bulánek, Roman (referee)
Heterogeneous catalysts for Meerwein-Ponndorf-Verley (MPV) reduction of ketones and aldehydes are investigated due to issues connected with water sensitivity and separation problems of homogeneous catalysts. During MPV reduction, a hydrogen atom is transferred from the sacrificial alcohol onto the carbonyl group of the ketone/aldehyde forming corresponding alcohol. Tin and zirconium containing zeolites are active catalysts in this hydrogen transfer reaction. However, when using conventional 3D zeolites in the reduction of bulky molecules, e.g., terpenoid compounds, problems with active site accessibility for these bulky reactants may arise. The use of 2D pillared zeolites may represent a solution to the diffusion problem. Silica metal-oxide pillars increase the distance between individual layers of a 2D (lamellar) zeolite and thus improve the active site accessibility. 2D catalysts were prepared by pillaring a parent lamellar pure-Si MFI with a mixture of tetraethyl orthosilicate and Zr (IV) isopropoxide or Sn (IV) isopropoxide, while conventional 3D zeolites were synthesised hydrothermally. The activity of Sn and Zr containing pillared catalysts was compared with the activity of the 3D MFI and beta zeolites in MPV reduction of furfural and citronellal. The 2D zeolites, however, did not facilitate...
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Design and catalytic application of novel nanostructured materials
Zhou, Yong ; Opanasenko, Maksym (advisor) ; Bulánek, Roman (referee) ; Zima, Vítězslav (referee)
Zeolites are crystalline aluminosilicates and environmentally friendly solid acid catalysts thanks to their non-toxicity, large surface area, excellent (hydro)thermal stability, and tunable acidity. Traditionally, zeolite catalysts are applied in industrial processes related to petrochemistry, but several studies have recently shown their high potential in fine chemicals production and volatile organic compounds (VOCs) elimination. Advanced materials based on newly developed layered and nanosized zeolites have exhibited further fascinating properties, e.g., a short diffusion pathway, tunable structure and morphology. However, the limited correlation between key parameters of zeolite synthesis and their properties (structural, textural, acidic) and catalytic performance, especially for new layered and nanosized zeolites, hinders the development and application of zeolite catalysts. Considering the above, this thesis focused on the preparation of several sets of specific zeolite catalysts to gain further insights into the relationship between key properties of zeolites (structure, morphology, chemical composition, accessibility to acid sites or other functional groups, and organization of layers, among others) and their performance as catalysts, supports for other active phases or nanosized...
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Ordering, transport and rotational dynamics of adsorbed carbon dioxide in metal-organic framework Zn2(BDC)2(DABCO)
Peksa, Mikuláš ; Lang, Jan (advisor) ; Bulánek, Roman (referee) ; Dračínský, Martin (referee)
The work analyzes the dynamics of carbon dioxide adsorbed in crystals of anisotropic metalo-organic frameworks Zn2(BDC)2(DABCO). It utilizes nuclear magnetic resonance methods, namely, the 13 C spetroscopy, the PFG method and the measurement of longitudinal relaxation times. Experimental data are compared with calculation of molecular dynamics. The thesis provides a theoretical model for explaining the temperature dependence of the residual anisotropy of the chemical shift observed in the spectra. The method of measuring diffusion anistropy based on the change of the shape of the 13 C spectra is described. The work determines the theoretical course of dependence of the longitudinal relaxation time on temperature using Redfield's theory. Times characterizing dynamic processes running on a picosecond scale that determine the dynamics of the fluid as a whole are evaluated from the data. 2
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Synthesis and Post-synthesis Modification of Novel 2-Dimensional Zeolites
Přech, Jan ; Čejka, Jiří (advisor) ; Bulánek, Roman (referee) ; Hronec, Mlan (referee)
Development of sustainable and environmentally friendly chemical processes is of vital importance nowadays. Although there is a palette of different synthetic methods for the formation of epoxides, sulphoxides and sulphones, from both economic and environmental points of view, a direct oxidation with a simple oxidant is highly appreciated. The main goals of the thesis were design and synthesis of novel titanium containing zeolitic materials with the ability to catalyse selective oxidation of sterically demanding organic compounds, particularly epoxidation of cyclic olefins and terpenes and oxidation of bulky thioethers to corresponding sulphoxides and sulphones with hydrogen peroxide as the oxidant. Two novel extra-large pore titanosilicates were prepared by means of hydrothermal synthesis (Ti-CFI, Ti-UTL), three large-pore titanosilicates (Ti-CON, Ti-AFI, Ti-IFR) were prepared using two step deboronation - liquid phase titanium impregnation procedure and two groups of lamellar materials were prepared. One group was based on modified nanosheet TS-1; the other was prepared from Ti-IPC- 1P lamellar precursor, which was prepared by means of top-down transformation of Ti-UTL. Last but not least, the Ti-UTL was transformed into new titanosilicates Ti-IPC-2 (OKO structure) and Ti-IPC-4 (PCR structure) by...
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Deposited palladium catalysts
Semler, Miloslav ; Štěpnička, Petr (advisor) ; Balcar, Hynek (referee) ; Bulánek, Roman (referee)
Palladium catalysts are frequently used in C-C coupling reactions. The aim of this work is to prepare several heterogeneous palladium catalysts from comercially available silica gel, each with different bifunctional ligand deposited on the surface of silica gel by N-propylamide linking group, and their testing on several C-C coupling reactions (Heck reaction, reaction of acyl chlorides with boronic acids and reaction of acyl chlorides with terminal acetylenes). Some other aspects of heterogeneous catalysis (such as palladium leaching into the reaction mixture and possibility of catalyst reuse) are discussed, too. Powered by TCPDF (www.tcpdf.org)
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